JP4607564B2 - Rubber composition and pneumatic tire using the same - Google Patents
Rubber composition and pneumatic tire using the same Download PDFInfo
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- JP4607564B2 JP4607564B2 JP2004353876A JP2004353876A JP4607564B2 JP 4607564 B2 JP4607564 B2 JP 4607564B2 JP 2004353876 A JP2004353876 A JP 2004353876A JP 2004353876 A JP2004353876 A JP 2004353876A JP 4607564 B2 JP4607564 B2 JP 4607564B2
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- 229920001971 elastomer Polymers 0.000 title claims description 69
- 239000005060 rubber Substances 0.000 title claims description 69
- 239000000203 mixture Substances 0.000 title claims description 47
- 239000006229 carbon black Substances 0.000 claims description 68
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 claims description 46
- 238000001179 sorption measurement Methods 0.000 claims description 43
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 38
- 239000011148 porous material Substances 0.000 claims description 30
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 29
- 229910052757 nitrogen Inorganic materials 0.000 claims description 19
- 238000010521 absorption reaction Methods 0.000 claims description 16
- 229920003244 diene elastomer Polymers 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 2
- 238000005096 rolling process Methods 0.000 description 27
- 238000000034 method Methods 0.000 description 8
- 239000002245 particle Substances 0.000 description 6
- 241000872198 Serjania polyphylla Species 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 4
- 229910052753 mercury Inorganic materials 0.000 description 4
- 238000005299 abrasion Methods 0.000 description 3
- 238000013329 compounding Methods 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 239000010419 fine particle Substances 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- 244000043261 Hevea brasiliensis Species 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229920003052 natural elastomer Polymers 0.000 description 2
- 229920001194 natural rubber Polymers 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 238000002459 porosimetry Methods 0.000 description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 description 2
- 239000005062 Polybutadiene Substances 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920001195 polyisoprene Polymers 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 239000012763 reinforcing filler Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T10/00—Road transport of goods or passengers
- Y02T10/80—Technologies aiming to reduce greenhouse gasses emissions common to all road transportation technologies
- Y02T10/86—Optimisation of rolling resistance, e.g. weight reduction
Landscapes
- Tires In General (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Description
本発明は、ゴム組成物及び該ゴム組成物を用いた空気入りタイヤに関し、特にタイヤのトレッドに適用することで、タイヤの耐摩耗性を向上させ、転がり抵抗を低減することが可能なゴム組成物に関するものである。 The present invention relates to a rubber composition and a pneumatic tire using the rubber composition, and particularly to a rubber composition that can be applied to a tread of a tire to improve the wear resistance of the tire and reduce rolling resistance. It is about things.
一般に、タイヤのトレッドには、高い耐摩耗性が要求されるため、トレッド用のゴム組成物には、補強性の高い充填剤としてカーボンブラックが配合される。また、使用するカーボンブラックの諸物性を選択することで、タイヤの諸性能を調節することができ、例えば、セチルトリメチルアンモニウムブロマイド（ＣＴＡＢ）吸着比表面積の大きいカーボンブラックを適用することで、カーボンブラックとゴム成分との接触面積を増加させることができ、また、ジブチルフタレート（ＤＢＰ）吸油量が高いカーボンブラックを適用することで、カーボンブラックとゴム成分との相互作用を増加させることができ、その結果として、ゴム組成物の耐摩耗性を向上させることができる。 In general, since a tire tread requires high wear resistance, carbon black is blended as a highly reinforcing filler in a rubber composition for a tread. In addition, various properties of the tire can be adjusted by selecting various physical properties of the carbon black to be used. For example, by applying carbon black having a large cetyltrimethylammonium bromide (CTAB) adsorption specific surface area, The contact area between the rubber component and the rubber component can be increased, and by applying carbon black having a high dibutyl phthalate (DBP) oil absorption, the interaction between the carbon black and the rubber component can be increased. As a result, the wear resistance of the rubber composition can be improved.
一方、近年、省エネルギー、省資源の社会的要請の下、自動車の燃料消費を節約するために、タイヤの転がり抵抗を低減することが求められるようになってきた。これに対して、トレッドに適用するゴム組成物の充填剤として、ＣＴＡＢ吸着比表面積の小さいカーボンブラックを適用して、カーボンブラックとゴム成分との接触面積を低減し、ＤＢＰ吸油量が少ないカーボンブラックを適用して、カーボンブラックとゴム成分との相互作用を低下させることで、タイヤの転がり抵抗を低減することができる。 On the other hand, in recent years, under the social demand for energy saving and resource saving, it has been required to reduce the rolling resistance of tires in order to save the fuel consumption of automobiles. On the other hand, carbon black having a small CTAB adsorption specific surface area is applied as a filler for the rubber composition applied to the tread, thereby reducing the contact area between the carbon black and the rubber component, and carbon black having a small DBP oil absorption. Is applied to reduce the interaction between the carbon black and the rubber component, thereby reducing the rolling resistance of the tire.
上述のように、トレッド用ゴム組成物に用いるカーボンブラックの性質を制御してタイヤの特性を制御する場合、耐摩耗性の向上と転がり抵抗の低減とは、二律背反の関係にあり、一般に、耐摩耗性を向上させつつ、転がり抵抗を低減することは困難である。 As described above, when controlling the properties of the tire by controlling the properties of the carbon black used in the rubber composition for treads, the improvement in wear resistance and the reduction in rolling resistance are in a trade-off relationship, and in general, It is difficult to reduce rolling resistance while improving wear.
これに対して、特公平６−４１５４０号公報（特許文献１）には、窒素吸着比表面積（Ｎ2ＳＡ）、ＤＢＰ吸油量及び凝集体空隙容積が特定の範囲にあるカーボンブラックを適用することで、耐摩耗性及び低発熱性に優れたゴム組成物が得られることが開示されている。 On the other hand, Japanese Patent Publication No. 6-41540 (Patent Document 1) applies carbon black having a specific range of nitrogen adsorption specific surface area (N 2 SA), DBP oil absorption amount and aggregate void volume. Thus, it is disclosed that a rubber composition excellent in wear resistance and low heat build-up can be obtained.
また、特開平３−１４９２３６号公報（特許文献２）には、水銀ポロシメーター法による細孔容積と水銀ポロシメーター法における細孔分布の最大ピークを占める細孔の容積とが特定の範囲にあるカーボンブラックを適用することで、補強性及び低発熱性が改善されたゴム組成物が得られることが開示されている。 Japanese Patent Application Laid-Open No. 3-149236 (Patent Document 2) discloses a carbon black in which the pore volume by the mercury porosimeter method and the volume of the pores occupying the maximum peak of the pore distribution by the mercury porosimeter method are in a specific range. It is disclosed that a rubber composition with improved reinforcement and low heat build-up can be obtained by applying.
しかしながら、特公平６−４１５４０号公報及び特開平３−１４９２３６号公報に開示の技術をもってしても、耐摩耗性と転がり抵抗とを高度にバランスすることは難しく、依然として改善の余地があった。 However, even with the techniques disclosed in Japanese Patent Publication No. 6-41540 and Japanese Patent Application Laid-Open No. 3-149236, it is difficult to achieve a high balance between wear resistance and rolling resistance, and there is still room for improvement.
そこで、本発明の目的は、上記従来技術の問題を解決し、タイヤの耐摩耗性を向上させると同時に、タイヤの転がり抵抗を低減することが可能なゴム組成物を提供することにある。また、本発明の他の目的は、かかるゴム組成物を用いた耐摩耗性に優れ、転がり抵抗が低い空気入りタイヤを提供することにある。 Therefore, an object of the present invention is to provide a rubber composition capable of solving the above-described problems of the prior art and improving the tire wear resistance and at the same time reducing the rolling resistance of the tire. Another object of the present invention is to provide a pneumatic tire having excellent wear resistance and low rolling resistance using such a rubber composition.
本発明者は、上記目的を達成するために鋭意検討した結果、タイヤのトレッド用ゴム組成物に、細孔容積が大きく、窒素吸着等温線から算出した細孔容積とＣＴＡＢ吸着比表面積とが特定の関係式を満たすカーボンブラックを充填剤として使用することで、タイヤの耐摩耗性を向上させつつ、転がり抵抗を低減できることを見出し、本発明を完成させるに至った。 As a result of intensive studies to achieve the above object, the present inventor has determined that the rubber composition for tire tread has a large pore volume and the pore volume calculated from the nitrogen adsorption isotherm and the CTAB adsorption specific surface area. By using carbon black satisfying this relational expression as a filler, it was found that rolling resistance can be reduced while improving the wear resistance of the tire, and the present invention has been completed.
即ち、本発明のゴム組成物は、ジエン系ゴムを含むゴム成分100質量部に対して、ＣＴＡＢ吸着比表面積が75〜150 m 2 /gで、ジブチルフタレート（ＤＢＰ）吸油量が140〜220 mL/100gで、且つ窒素吸着等温線から算出した細孔容積とセチルトリメチルアンモニウムブロマイド（ＣＴＡＢ）吸着比表面積とが下記式(I)：
Ｙ ＞ 0.0071 × Ｘ ＋ 0.03 ・・・ (I)
［式中、Ｙは窒素吸着等温線から算出した細孔容積（cc/g）であり、ＸはＣＴＡＢ吸着比表面積（m2/g）である］の関係を満たすカーボンブラックを10〜100質量部配合してなることを特徴とする。ここで、カーボンブラックの細孔容積は、乾燥後のカーボンブラックに対し77Ｋで窒素吸着等温線を測定し、該窒素吸着等温線から算出した値であり、また、カーボンブラックのＣＴＡＢ吸着比表面積は、ＩＳＯ６８１０法に準拠して測定された値である。
That is, the rubber composition of the present invention has a CTAB adsorption specific surface area of 75 to 150 m 2 / g and a dibutyl phthalate (DBP) oil absorption of 140 to 220 mL with respect to 100 parts by mass of the rubber component containing the diene rubber. / 100 g and the pore volume calculated from the nitrogen adsorption isotherm and the cetyltrimethylammonium bromide (CTAB) adsorption specific surface area are represented by the following formula (I):
Y> 0.0071 × X + 0.03 (I)
10 to 100 mass of carbon black satisfying the relationship [where Y is the pore volume (cc / g) calculated from the nitrogen adsorption isotherm, and X is the CTAB adsorption specific surface area (m 2 / g)] and characterized by being part formulation. Here, the pore volume of carbon black is a value obtained by measuring a nitrogen adsorption isotherm at 77 K with respect to the carbon black after drying, and calculating from the nitrogen adsorption isotherm, and the CTAB adsorption specific surface area of carbon black is , Measured in accordance with ISO 6810 method.
本発明のゴム組成物において、前記カーボンブラックは、ＣＴＡＢ吸着比表面積が75〜150 m2/gで且つジブチルフタレート（ＤＢＰ）吸油量が140〜220 mL/100gである。この場合、ゴム組成物の加工性を悪化させることなく、該ゴム組成物を用いたタイヤの耐摩耗性を大幅に向上させることができ、また、タイヤの転がり抵抗の悪化も防止できる。 In the rubber composition of the present invention, the carbon black, CTAB adsorption specific surface area and dibutyl phthalate at 75~150 m 2 / g (DBP) oil absorption amount is 140 to 220 mL / 100 g. In this case, the wear resistance of a tire using the rubber composition can be greatly improved without deteriorating the workability of the rubber composition, and the deterioration of the rolling resistance of the tire can be prevented.
本発明のゴム組成物においては、前記ゴム成分が前記ジエン系ゴムを10質量％以上含むことが好ましく、また、前記カーボンブラックの配合量が前記ゴム成分100質量部に対して10〜100質量部である。 In the rubber composition of the present invention, the rubber component preferably contains 10% by mass or more of the diene rubber, and the amount of the carbon black is 10 to 100 parts by mass with respect to 100 parts by mass of the rubber component. It is .
また、本発明の空気入りタイヤは、上記ゴム組成物をタイヤ部材のいずれかに適用したことを特徴とする。ここで、前記タイヤ部材がトレッドであることが好ましい。 The pneumatic tire of the present invention is characterized in that the rubber composition is applied to any of tire members. Here, the tire member is preferably a tread.
本発明によれば、窒素吸着等温線から算出した細孔容積とＣＴＡＢ吸着比表面積とが特定の関係式を満たすカーボンブラックを充填剤として使用することで、タイヤの耐摩耗性を向上させつつ、転がり抵抗を低減することが可能なゴム組成物を提供することができる。また、かかるゴム組成物を用いた、耐摩耗性に優れ、転がり抵抗が低い空気入りタイヤを提供することができる。 According to the present invention, using carbon black satisfying a specific relational expression between the pore volume calculated from the nitrogen adsorption isotherm and the CTAB adsorption specific surface area as a filler, while improving the wear resistance of the tire, A rubber composition capable of reducing rolling resistance can be provided. Moreover, the pneumatic tire using this rubber composition, which has excellent wear resistance and low rolling resistance, can be provided.
以下に、本発明を詳細に説明する。本発明のゴム組成物は、ジエン系ゴムを含むゴム成分100質量部に対して、ＣＴＡＢ吸着比表面積が75〜150 m 2 /gで、ジブチルフタレート（ＤＢＰ）吸油量が140〜220 mL/100gで、且つ窒素吸着等温線から算出した細孔容積とセチルトリメチルアンモニウムブロマイド（ＣＴＡＢ）吸着比表面積とが絶対値として下記式(I)：
Ｙ ＞ 0.0071 × Ｘ ＋ 0.03 ・・・ (I)
［式中、Ｙは窒素吸着等温線から算出した細孔容積（cc/g）であり、ＸはＣＴＡＢ吸着比表面積（m2/g）である］の関係を満たすカーボンブラックを10〜100質量部配合してなる。
The present invention is described in detail below. The rubber composition of the present invention has a CTAB adsorption specific surface area of 75 to 150 m 2 / g and a dibutyl phthalate (DBP) oil absorption of 140 to 220 mL / 100 g with respect to 100 parts by mass of a rubber component containing a diene rubber. And the pore volume calculated from the nitrogen adsorption isotherm and the cetyltrimethylammonium bromide (CTAB) adsorption specific surface area as absolute values of the following formula (I):
Y> 0.0071 × X + 0.03 (I)
10 to 100 mass of carbon black satisfying the relationship [where Y is the pore volume (cc / g) calculated from the nitrogen adsorption isotherm, and X is the CTAB adsorption specific surface area (m 2 / g)] part blended composed.
一般に、カーボンブラックの粒径を小さくすることで、カーボンブラックの粒子間の容積が増加して、カーボンブラックとゴム成分との接触面積が増加するため、微粒径のカーボンブラックを適用することで、ゴム組成物の耐摩耗性を向上させることができる。しかしながら、該微粒径のカーボンブラックは、ゴム成分との接触面積が大きいため、該微粒径のカーボンブラックを配合したゴム組成物をタイヤに適用すると、タイヤの転がり抵抗が上昇してしまう。そのため、微粒径のカーボンブラックを用いたのでは、耐摩耗性と転がり抵抗を同時に改善することができない。これに対して、本発明では、同等の粒子径を有するカーボンブラックにおいて、窒素吸着等温線から算出した細孔容積を増加させることで、カーボンブラックの細孔内に拘束されるゴム成分の量を増加させて、耐摩耗性を向上させる。また、驚くべきことに、同等の粒子径を有するカーボンブラックにおいて、窒素吸着等温線から算出した細孔容積を増加させても、タイヤの転がり抵抗を上昇させることがなかった。 In general, reducing the particle size of carbon black increases the volume between carbon black particles and increases the contact area between the carbon black and the rubber component. The abrasion resistance of the rubber composition can be improved. However, since the fine particle size carbon black has a large contact area with the rubber component, when a rubber composition containing the fine particle size carbon black is applied to a tire, the rolling resistance of the tire increases. Therefore, if carbon black having a fine particle size is used, the wear resistance and rolling resistance cannot be improved at the same time. On the other hand, in the present invention, in carbon black having an equivalent particle diameter, the amount of the rubber component restrained in the pores of the carbon black is increased by increasing the pore volume calculated from the nitrogen adsorption isotherm. Increase the wear resistance. Surprisingly, in carbon black having the same particle size, even when the pore volume calculated from the nitrogen adsorption isotherm was increased, the rolling resistance of the tire was not increased.
なお、従来、カーボンブラックの細孔容積は、水銀圧入法で測定されており、水銀圧入法による測定値はメソ細孔（0.05〜0.002μm）からマクロ細孔（0.05μm以上）の容積であるため、該細孔容積は、カーボンブラックの粒子間の細孔容積を求めたものである。これに対し、本発明では、カーボンブラックの細孔容積を窒素吸着等温線から算出し、その測定値はミクロ細孔（2nm以下）からメソ細孔（0.05〜0.002μm）の容積であるため、窒素吸着等温線から算出した細孔容積は、カーボンブラックの一次粒子自身の細孔容積を求めたものである。上述のように、本発明では、カーボンブラックの細孔内に拘束されるゴム成分の量を増加させて、耐摩耗性を向上させるため、窒素吸着等温線から算出した細孔容積Ｙが式(I)の関係を満たすカーボンブラックを用いる。また、式(I)中のＣＴＡＢ吸着比表面積Ｘは、カーボンブラックの微細孔を含まない外部表面積を測定した値であるため、式(I)の関係を満たすカーボンブラックは、通常のカーボンブラックよりも細孔容積が大きく、細孔内に拘束するゴム成分の量が多く、ゴム組成物の耐摩耗性を向上させる効果が大きい。 Conventionally, the pore volume of carbon black has been measured by mercury porosimetry, and the measured value by mercury porosimetry is the volume from mesopores (0.05 to 0.002 μm) to macropores (0.05 μm or more). Therefore, the pore volume is obtained by determining the pore volume between carbon black particles. On the other hand, in the present invention, the pore volume of carbon black is calculated from the nitrogen adsorption isotherm, and the measured value is the volume from micropores (2 nm or less) to mesopores (0.05 to 0.002 μm). The pore volume calculated from the nitrogen adsorption isotherm is obtained from the pore volume of the carbon black primary particles themselves. As described above, in the present invention, the pore volume Y calculated from the nitrogen adsorption isotherm is expressed by the following formula in order to increase the amount of the rubber component restrained in the pores of the carbon black and improve the wear resistance. Carbon black satisfying the relationship of I) is used. In addition, since the CTAB adsorption specific surface area X in the formula (I) is a value obtained by measuring the external surface area that does not contain the fine pores of the carbon black, the carbon black satisfying the relationship of the formula (I) is more than ordinary carbon black. However, the pore volume is large, the amount of the rubber component restrained in the pores is large, and the effect of improving the wear resistance of the rubber composition is great.
上記カーボンブラックは、ＣＴＡＢ吸着比表面積が75〜150 m2/gであり、80〜140 m2/gであることが好ましい。ＣＴＡＢ吸着比表面積が75 m2/g未満のカーボンブラックを用いると、ゴム組成物の耐摩耗性が大幅に悪化し、一方、ＣＴＡＢ吸着比表面積が150 m2/gを超えるカーボンブラックを配合したゴム組成物をタイヤに用いると、タイヤの転がり抵抗が大幅に悪化する上、カーボンブラックの粒径が小さ過ぎるため、カーボンブラックのゴム成分への分散性が低下し、耐摩耗性を十分に向上させることができない。ここで、ＣＴＡＢ吸着比表面積が80〜140 m2/gのカーボンブラックを用いることで、転がり抵抗の悪化を防止しつつ、耐摩耗性を大幅に向上させることができる。 The carbon black has a CTAB adsorption specific surface area of 75 to 150 m 2 / g , and preferably 80 to 140 m 2 / g. When carbon black with a CTAB adsorption specific surface area of less than 75 m 2 / g was used, the wear resistance of the rubber composition was greatly deteriorated, while carbon black with a CTAB adsorption specific surface area of over 150 m 2 / g was blended. When the rubber composition is used in a tire, the rolling resistance of the tire is greatly deteriorated and the particle size of the carbon black is too small, so that the dispersibility of the carbon black in the rubber component is lowered and the wear resistance is sufficiently improved. I can't let you. Here, by using carbon black having a CTAB adsorption specific surface area of 80 to 140 m 2 / g, wear resistance can be greatly improved while preventing deterioration of rolling resistance.
また、上記カーボンブラックは、ジブチルフタレート（ＤＢＰ）吸油量が140〜220 mL/100gであり、145〜200 mL/100gであることが好ましく、150〜195 mL/100gであることがより一層好ましい。ＤＢＰ吸油量が140 mL/100g未満のカーボンブラックを用いると、ゴム組成物の耐摩耗性が悪化し、一方、ＤＢＰ吸油量が220 mL/100gを超えるカーボンブラックを用いると、ゴム組成物の加工性が悪化する。 The carbon black has a dibutyl phthalate (DBP) oil absorption of 140 to 220 mL / 100 g , preferably 145 to 200 mL / 100 g, and more preferably 150 to 195 mL / 100 g. When carbon black with a DBP oil absorption of less than 140 mL / 100 g is used, the wear resistance of the rubber composition deteriorates, whereas when carbon black with a DBP oil absorption of over 220 mL / 100 g is used, the rubber composition is processed. Sex worsens.
上記カーボンブラックの配合量は、後述するゴム成分100質量部に対して10〜100質量部の範囲である。上記カーボンブラックの配合量がゴム成分100質量部に対して10質量部未満では、ゴム組成物の耐摩耗性が低下することがあり、100質量部を超えると、ゴム組成物の低発熱性が低下して、該ゴム組成物を用いたタイヤの転がり抵抗が上昇し、低燃費性が悪化することがある。
The amount of the carbon black is in the range of 10 to 100 parts by mass with respect to 100 parts by mass of the rubber component described later. When the amount of the carbon black is less than 10 parts by mass with respect to 100 parts by mass of the rubber component, the wear resistance of the rubber composition may be reduced. When the amount exceeds 100 parts by mass, the low exothermic property of the rubber composition is reduced. The rolling resistance of the tire using the rubber composition may be increased and the fuel efficiency may be deteriorated.
上記諸物性を有するカーボンブラックは、例えば、カーボンブラック製造炉における空気導入条件、原料油導入条件、並びに反応停止のために導入する水の導入位置、導入量及びその後の温度等を調整することで製造できる。 The carbon black having various physical properties described above can be adjusted, for example, by adjusting the air introduction conditions, the feedstock introduction conditions, the introduction position of water to be introduced for stopping the reaction, the introduction amount, the subsequent temperature, etc. in the carbon black production furnace. Can be manufactured.
本発明のゴム組成物のゴム成分は、少なくともジエン系ゴムを含むことを要し、該ジエン系ゴムを10質量％以上含むことが好ましい。ここで、ジエン系ゴムとしては、天然ゴム（ＮＲ）の他、ポリイソプレンゴム（ＩＲ）、スチレン・ブタジエン共重合体ゴム（ＳＢＲ）、ポリブタジエンゴム（ＢＲ）等のジエン系合成ゴムが挙げられる。なお、これらゴム成分は、１種単独で用いてもよいし、２種以上のブレンドとして用いてもよい。 The rubber component of the rubber composition of the present invention needs to contain at least a diene rubber, and preferably contains 10% by mass or more of the diene rubber. Here, examples of the diene rubber include natural rubber (NR) and diene synthetic rubbers such as polyisoprene rubber (IR), styrene / butadiene copolymer rubber (SBR), and polybutadiene rubber (BR). These rubber components may be used alone or in a blend of two or more.
本発明のゴム組成物には、上記カーボンブラックの他に、老化防止剤、加硫剤、加硫促進剤、酸化亜鉛、ステアリン酸等のゴム業界で通常使用される配合剤を、本発明の目的を害しない範囲内で適宜選択して配合することができる。これら配合剤としては、市販品を好適に使用することができる。また、上記ゴム組成物は、ゴム成分に対し、カーボンブラックと、適宜選択した各種配合剤とを配合して、混練り、熱入れ、押出等することにより製造することができる。 In the rubber composition of the present invention, in addition to the above carbon black, compounding agents usually used in the rubber industry such as anti-aging agent, vulcanizing agent, vulcanization accelerator, zinc oxide, stearic acid, etc. It can be appropriately selected and blended within a range that does not impair the purpose. As these compounding agents, commercially available products can be suitably used. Further, the rubber composition can be produced by blending carbon black and various appropriately selected compounding ingredients with a rubber component, kneading, heating, extruding, and the like.
本発明の空気入りタイヤは、上記ゴム組成物をタイヤ部材のいずれかに適用したことを特徴とする。ここで、本発明のタイヤにおいては、上記ゴム組成物をトレッドに用いることが特に好ましく、上記ゴム組成物をトレッドに用いたタイヤは、耐摩耗性に優れる上、転がり抵抗が低く、低燃費性に優れる。なお、本発明のタイヤに充填する気体としては、通常の或いは酸素分圧を変えた空気、又は窒素等の不活性ガスが挙げられる。 The pneumatic tire of the present invention is characterized in that the rubber composition is applied to any of tire members. Here, in the tire of the present invention, it is particularly preferable to use the rubber composition for a tread. The tire using the rubber composition for a tread has excellent wear resistance, low rolling resistance, and low fuel consumption. Excellent. In addition, as gas with which the tire of the present invention is filled, normal or air with a changed oxygen partial pressure, or an inert gas such as nitrogen is exemplified.
以下に、実施例を挙げて本発明を更に詳しく説明するが、本発明は下記の実施例に何ら限定されるものではない。 Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to the following examples.
＜カーボンブラックの製造例＞
表１に示す条件でカーボンブラックをそれぞれ製造した。
Carbon black was produced under the conditions shown in Table 1.
上記カーボンブラックを用い、バンバリーミキサーで混練して、表２に示す配合処方のゴム組成物を調製した。また、各ゴム組成物に使用したカーボンブラックのＣＴＡＢ吸着比表面積、ＤＢＰ吸油量及び細孔容積を下記の方法で測定した。結果を表１及び表３に示す。 The carbon black was kneaded with a Banbury mixer to prepare a rubber composition having the formulation shown in Table 2. Moreover, the CTAB adsorption specific surface area, DBP oil absorption amount and pore volume of carbon black used in each rubber composition were measured by the following methods. The results are shown in Tables 1 and 3.
（１）ＣＴＡＢ吸着比表面積
ＩＳＯ６８１０法に準拠して、各カーボンブラックの単位質量当りの比表面積（m2/g）を測定した。
(1) CTAB adsorption specific surface area Based on the ISO6810 method, the specific surface area (m 2 / g) per unit mass of each carbon black was measured.
（２）ＤＢＰ吸油量
ＩＳＯ４６５６−１法に準拠して、各カーボンブラックの100g当りのジブチルフタレート（ＤＢＰ）吸収量（mL）を測定した。
(2) DBP oil absorption The amount of dibutyl phthalate (DBP) absorption (mL) per 100 g of each carbon black was measured according to the ISO4656-1 method.
（３）細孔容積
200mgのカーボンブラックを2時間真空乾燥後、77Ｋ（-196℃）の下（Ｎ2相対圧＝0.995）で窒素吸着等温線を測定し、該窒素吸着等温線から細孔容積を算出した。
(3) Pore volume
After 200 mg of carbon black was vacuum dried for 2 hours, a nitrogen adsorption isotherm was measured under 77 K (−196 ° C.) (N 2 relative pressure = 0.95), and the pore volume was calculated from the nitrogen adsorption isotherm.
*1 詳細を表３に示す。
*2 Ｎ-ｔ-ブチル-２-ベンゾチアゾリルスルフェンアミド.
* 1 Details are shown in Table 3.
* 2 Nt-butyl-2-benzothiazolylsulfenamide.
次に、得られたゴム組成物をトレッドに用いて、サイズ１１Ｒ２２.５のトラック用タイヤを試作し、下記の方法で該タイヤの耐摩耗性及び転がり抵抗を評価した。結果を表３に示す。 Next, using the obtained rubber composition as a tread, a truck tire of size 11R22.5 was prototyped, and the wear resistance and rolling resistance of the tire were evaluated by the following methods. The results are shown in Table 3.
（４）タイヤの耐摩耗性
上記トラック用タイヤを車両に装着し、4万km走行した時点でのタイヤの溝の減量を測定し、従来例のタイヤの溝減量の逆数を100として指数表示した。指数値が大きい程、耐摩耗性に優れることを示す。
(4) Abrasion resistance of tires The above tires for trucks were mounted on a vehicle, and the amount of tire groove loss at the time of 40,000 km travel was measured. . It shows that it is excellent in abrasion resistance, so that an index value is large.
（５）タイヤの転がり抵抗
上記トラック用タイヤをドラム上でフリー回転させ、転がり抵抗を測定した。また、得られた転がり抵抗値を、次式：
転がり抵抗指数＝対象タイヤの転がり抵抗／従来例タイヤの転がり抵抗×100
に従って指数表示した。指数値が小さい程、転がり抵抗が小さく、良好であることを示す。
(5) Rolling resistance of tire The above-mentioned truck tire was freely rotated on a drum, and the rolling resistance was measured. Also, the obtained rolling resistance value is expressed by the following formula:
Rolling resistance index = rolling resistance of the target tire / rolling resistance of conventional tire x 100
According to the index. The smaller the index value, the smaller the rolling resistance and the better.
比較例２で用いたカーボンブラックは、実施例２で用いたカーボンブラックとＣＴＡＢ吸着比表面積及びＤＢＰ吸油量がほぼ同等であるが、上記式(I)の関係式を満たさないため、比較例２のタイヤは、実施例２のタイヤに比べ、耐摩耗性が悪化していた。 The carbon black used in Comparative Example 2 has almost the same CTAB adsorption specific surface area and DBP oil absorption as the carbon black used in Example 2, but does not satisfy the relational expression of the above formula (I). The tire of No. 2 had deteriorated wear resistance as compared with the tire of Example 2.
また、比較例３で用いたカーボンブラックは、実施例３で用いたカーボンブラックとＣＴＡＢ吸着比表面積がほぼ同等であるが、ＤＢＰ吸油量が小さ過ぎる上、上記式(I)の関係式を満たさないため、比較例３のタイヤは、実施例３のタイヤに比べ、耐摩耗性が大幅に悪化していた。 Further, the carbon black used in Comparative Example 3 has substantially the same CTAB adsorption specific surface area as the carbon black used in Example 3, but the DBP oil absorption is too small and satisfies the relational expression of the above formula (I). Therefore, the tire of Comparative Example 3 was significantly deteriorated in wear resistance as compared with the tire of Example 3.
なお、比較例１で用いたカーボンブラックは、実施例１で用いたカーボンブラックとＤＢＰ吸油量がほぼ同等であるものの、ＣＴＡＢ吸着比表面積が小さ過ぎるため、比較例１のタイヤは、実施例１のタイヤに比べ、耐摩耗性が悪化していた。 The carbon black used in Comparative Example 1 has almost the same DBP oil absorption as that of Carbon Black used in Example 1, but the CTAB adsorption specific surface area is too small. The wear resistance was worse than that of other tires.
Claims (4)
ＣＴＡＢ吸着比表面積が75〜150 m 2 /gで、ジブチルフタレート（ＤＢＰ）吸油量が140〜220 mL/100gで、且つ窒素吸着等温線から算出した細孔容積とセチルトリメチルアンモニウムブロマイド（ＣＴＡＢ）吸着比表面積とが下記式(I)：
Ｙ ＞ 0.0071 × Ｘ ＋ 0.03 ・・・ (I)
［式中、Ｙは窒素吸着等温線から算出した細孔容積（cc/g）であり、ＸはＣＴＡＢ吸着比表面積（m2/g）である］の関係を満たすカーボンブラックを10〜100質量部配合してなるゴム組成物。 For 100 parts by mass of rubber component including diene rubber,
CTAB adsorption specific surface area of 75-150 m 2 / g, dibutyl phthalate (DBP) oil absorption of 140-220 mL / 100 g, and pore volume calculated from nitrogen adsorption isotherm and cetyltrimethylammonium bromide (CTAB) adsorption The specific surface area is represented by the following formula (I):
Y> 0.0071 × X + 0.03 (I)
10 to 100 mass of carbon black satisfying the relationship [where Y is the pore volume (cc / g) calculated from the nitrogen adsorption isotherm, and X is the CTAB adsorption specific surface area (m 2 / g)] A rubber composition obtained by partially blending.
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